NOx emissions from diesel engines are an environmental problem. Several countries, including the United States, have long had regulations pending that will limit NOx emissions from trucks and other diesel-powered vehicles. Manufacturers and researchers have put considerable effort toward meeting those regulations.
In gasoline powered vehicles that use stoichiometric fuel-air mixtures, three-way catalysts have been shown to control NOX emissions. In diesel-powered vehicles, which use compression ignition, the exhaust is generally too oxygen-rich for three-way catalysts to be effective.
Several solutions have been proposed for controlling NOX emissions from diesel-powered vehicles. One set of approaches focuses on the engine. Techniques such as exhaust gas recirculation and partially homogenizing fuel-air mixtures are helpful, but these techniques alone will not eliminate NOX emissions. Another set of approaches remove NOX from the vehicle exhaust. These include the use of lean-burn NOX catalysts, selective catalytic reduction (SCR) catalysts, and lean NOX traps (LNTs).
Lean-burn NOX catalysts promote the reduction of NOx under oxygen-rich conditions. Reduction of NOX in an oxidizing atmosphere is difficult. It has proven challenging to find a lean-burn NOx catalyst that has the required activity, durability, and operating temperature range. A reductant such as diesel fuel must be steadily supplied to the exhaust for lean NOX reduction, introducing a fuel economy penalty of 3% or more. Currently, peak NOX conversion efficiencies for lean-burn NOX catalysts are unacceptably low.
SCR generally refers to selective catalytic reduction of NOX by ammonia. The reaction takes place even in an oxidizing environment. The NOX can be temporarily stored in an adsorbent or ammonia can be fed continuously into the exhaust. SCR can achieve high levels of NOX reduction, but there is a disadvantage in the lack of infrastructure for distributing ammonia or a suitable precursor. Another concern relates to the possible release of ammonia into the environment.
LNTs are devices that adsorb NOX under lean exhaust conditions and reduce and release the adsorbed NOX under rich conditions. An LNT generally includes a NOX adsorbent and a catalyst. The adsorbent is typically an alkaline earth compound, such as BaCO3 and the catalyst is typically a combination of precious metals including Pt and Rh. In lean exhaust, the catalyst speeds oxidizing reactions that lead to NOX adsorption. In a reducing environment, the catalyst activates reactions by which hydrocarbon reductants are converted to more active species, the water-gas shift reaction, which produces more active hydrogen from less active CO, and reactions by which adsorbed NOX is reduced and desorbed. In a typical operating protocol, a reducing environment will be created within the exhaust from time-to-time to regenerate (denitrate) the LNT.
Regeneration to remove accumulated NOx may be referred to as denitration in order to distinguish desulfation, which is carried out much less frequently. The reducing environment for denitration can be created in several ways. One approach uses the engine to create a rich exhaust-reductant mixture. For example, the engine can inject extra fuel into the exhaust within one or more cylinders prior to expelling the exhaust. A reducing environment can also be created by injecting a reductant into lean exhaust downstream from the engine. In either case, a portion of the reductant is generally expended to consume excess oxygen in the exhaust. To lessen the amount of excess oxygen and reduce the amount of reductant expended consuming excess oxygen, the engine may be throttled, although such throttling may have an adverse effect on the performance of some engines.
Reductant can consume excess oxygen by either combustion or reforming reactions. Typically, the reactions take place upstream of the LNT over an oxidation catalyst or in a fuel reformer. The reductant can also be oxidized directly in the LNT, but this tends to result in faster thermal aging. U.S. Pat. Pub. No. 2004/0050037 (hereinafter “the '037 publication”) describes an exhaust system with a fuel reformer placed in an exhaust line upstream from an LNT. The reformer includes both oxidation and reforming catalysts. The reformer both removes excess oxygen and converts the diesel fuel reductant into more reactive reformate.
The oxidation and reforming catalysts of the '037 publication are subject to harsh conditions. According the '037 publication, it is desirable to heat the fuel reformer to steam reforming temperatures for each LNT regeneration and to pulse the fuel injection during regeneration to prevent the fuel reformer from overheating. Pulsing causes the catalyst to alternate between lean and rich conditions while at high temperature. The catalyst itself tends to undergo chemical changes through this cycling, which can lead to physical changes, especially sintering, which is the growth of catalyst particles. As the particles grow, their surface area and number of surface atoms decrease, resulting in a less active catalyst.
Numerous choices are available for the oxidation and reforming catalysts, With regard to the oxidation catalyst, the '037 patent lists Pd, Pt, Ir, Rh, Cu, Co, Fe, Ni, Ir, Cr, and Mo as possible choices, without limitation. The catalyst support is also important. The '037 patent lists as examples, without limitation, cerium zirconium oxide mixtures or solid solutions, silica alumina, Ca, Ba, Si, or La stabilized alumina. Many other oxidation catalysts, supports, and stabilizers are known in the art. Likewise, many examples or reforming catalysts are known. The '037 patent list Ni, Rh, Pd, and Pt as possible reforming catalysts, without limitation. As with the oxidation catalyst, a wide range of supports and stabilizers could be considered for use.
In spite of advances, there continues to be a long felt need for an affordable and reliable diesel exhaust aftertreatment system that is durable, has a manageable operating cost (including fuel penalty), and reduces NOX emissions to a satisfactory extent in the sense of meeting U.S. Environmental Protection Agency (EPA) regulations effective in 2010 and other such regulations.